Removal of humic substances by biosorption

Fungal pellets of Aspergillus niger 405,Aspergillus ustus 326,and Stachybotrys sp.1103 were used for the removal of humic substances from aqueous solutions.Batchwise biosorption,carried out at pH 6 and 25°C,was monitored spectrophotometrically and the process described with Freundlich’s model.Calculated sorption coeffcients Kf and n showed that A.niger exhibited the highest effciency.A good match between the model and experimental data and a high correlation coeffcient(R2)pointed out to judicious choice of ...     

A chemical structure for humic substances

Dedicated to Prof. Dr. H. D. Beckey on the occasion of his 70th birthday.     

腐殖酸结合汞在土壤中的分布特征

采集了四川省内有代表性的26个土壤,对腐殖酸结合汞在土壤中的水平分布和在土壤剖面中的垂直分布进行了分析讨论.结果表明,腐殖酸结合汞及其两组分在土壤中的分布受到内在物源腐殖酸和外来汞源的决定性影响,以及土壤性质的影响.腐殖酸结合汞(HAs-Hg)和组分胡敏酸结合汞(HA-Hg)在不同土纲土壤中以淋溶土纲含量最高,其次是半水成土纲和初育土纲,最低是铁铝土纲;组分富里酸结合汞(FA-Hg)的含量以在半水成土纲中最低.在土壤剖面中,表现为土层越深,HAs-Hg与两组分含量、HA-Hg/FA-Hg比例越低.     

Polymerization of humic substances by an enzyme-catalyzed oxidative coupling

 A novel understanding of the structural features of humic substances supports the self-assembly supramolecular association of relatively small molecules rather than their polymeric nature. An increase in the conformational stability of humus may thus be achieved through promotion of intermolecular covalent bondings between heterogeneous humic molecules by an enzyme-catalyzed oxidative reaction. We present evidence from high performance size exclusion chromatography (HPSEC) and diffuse reflectance infrared spectrometry (DRIFT) that oxidation of a humic material catalyzed by horseradish peroxidase stabilizes the humic structure by the formation of aryl and alkyl ethers and permanently enhances its molecular size. Received: 15 May 2000 / Accepted in revised form: 14 July 2000     

Interaction of humic substances and hematite: FTIR study

IntroductionInteractionsofhumicsubstances(HSs)andironoxidesareofgreatsignificanceinmanygeochemicalprocesses.ItisclearthatadsorptionofHSstothesurfaceofironoxidescangreatlyinfluencethepropertiesofsuchsurfaces,thuspotentialaffectthefate,behavior,transportandtransformationofenvironmentalpollutants(Mcknight,1992).Ononehand,whenadsorbedtosurfacesofironoxides,HSsmaybindandhenceimmobilizetracemetals,radionucilides,andnonionicorganicpollutants,andtheyalsoalteroxidesurfacechargepropertiesandflocculat…     

Fenton试剂氧化降解腐殖酸动力学

研究了Fenton试剂氧化降解腐殖酸废水的过程及动力学.结果表明,Fenton法能通过氧化和混凝作用有效去除腐殖酸,其中氧化降解速率主要与Fenton试剂投量、腐殖酸初始浓度和初始pH值有关,且氧化作用主要发生在反应前60 min.在pH为4.0,[Fe2+]0为5～40 mmol.L-1,[H2O2]0为40～120 mmol.L-1,[HS]0为250～1 000 mg.L-1,温度为278～318 K的实验范围内,反应初始阶段腐殖酸的氧化降解符合表观反应动力学模型.模型值与实验值吻合良好,说明该反应动力学模型能较好地描述Fenton氧化降解腐殖酸过程.Fenton氧化降解腐殖酸的初始反应活化能Ea为14.9 kJ.mol-1,说明反应较易进行.动力学模型的反应总级数为2.34,其中H2O2的反应分级数(0.86)高于Fe2+的分级数(0.47),表明H2O2浓度比Fe2+浓度对Fenton氧化降解反应的影响大.     

Molecular structures and associations of humic substances in the terrestrial environment

Here we show, for the first time, evidence of the primary molecular structures in humic substances (HS), the most abundant naturally occurring organic molecules on Earth, and their associations as mixtures in terrestrial systems. Multi-dimensional nuclear magnetic resonance (NMR) experiments show us that the major molecular structural components in the mixtures operationally defined as HS are aliphatic acids, ethers, esters and alcohols; aromatic lignin derived fragments; polysaccharides and polypeptides. By means of diffusion ordered spectroscopy, distinct diffusion coefficients consistent with relatively low molecular weight molecules were observed for all the components in the mixtures, and saccharides were the largest single class of component present. Liquid chromatography NMR confirmed that HS components can be easily separated and nuclear Overhauser effect (NOE) enhancements support the finding that the components are of relatively low molecular weight <~2,000 Da. The widely recognized properties of HS, i.e., characteristics indicative of crosslinked, macromolecular networks, can now be explained as aggregation of mixtures, most likely instigated by complexation with metal cations.     

Effect of humic substances on the precipitation of calcium phosphate

For phosphorus （P） recovery from wastewater, the effect of humic substances （HS） on the precipitation of calcium phosphate was studied. Batch experiments of calcium phosphate precipitation were undertaken with synthetic water that contained 20 mg/L phosphate （as P） and 20 mg/L HS （as dissolved organic carbon, DOC） at a constant pH value in the range of 8.0-10.0. The concentration variations of phosphate, calcium （Ca） and HS were measured in the precipitation process; the crystalline state and compositions of the precipitates were analysed by powder X-ray diffraction （XRD） and chemical methods, respectively. It showed that at solution pH 8.0, the precipitation rate and removal efficiency of phosphate were greatly reduced by HS, but at solution pH ≥9.0, the effect of HS was very small. The Ca consumption for the precipitation of phosphate increased when HS was added; HS was also removed from solution with the precipitation of calcium phosphate. At solution pH 8.0 and HS concentrations ≤3.5 mg/L, and at pH ≥ 9.0 and HS concentrations ≤ 10 mg/L, the final precipitates were proved to be hydroxyapatite （HAP） by XRD. The increases of solution pH value and initial Ca/P ratio helped reduce the influence of HS on the precipitation of phosphate.     

腐殖质及其模型化合物的H2O2光化学生成研究

在模拟太阳光下研究了多种腐殖质及其模型化合物的过氧化氢（H₂O₂）生成动力学,并对其生成机制进行了探讨.结果表明不同来源或不同形式的腐殖质在模拟太阳光照射下均能产生H₂O₂.不同腐殖质生成H₂O₂速率差异不大,范围为6.379~15.784nmol/（L·min）,腐殖酸生成H₂O₂速率略快于富里酸.对于腐殖质模型化合物,邻苯二酚、间苯二酚、对苯二酚、苯醌、邻茴香胺、对茴香胺、水杨酸和2,6-二甲氧基-1,4-苯醌等8种模型化合物没有产生明显的H₂O₂,而藜芦醇、对氨基苯甲酸、3,5-二羟基苯甲酸（DHBA）、2,5-二羟基-1,4-苯醌、苯酚、苯甲酸和苯胺等7种化合物均可检测到H₂O₂产生.但其产生H₂O₂的速率差异较大,相差1~2个数量级,生成H₂O₂速率最快的化合物为2,5-二羟基-1,4-苯醌和DHBA,较慢的为苯酚、苯甲酸和对氨基苯甲酸.基于腐殖质生成H₂O₂机制,推测典型模型化合物DHBA的H₂O₂生成机制可能为光照条件下该化合物跃迁为单重激发态,该激发态发生分子内电子转移,生成还原性自由基中间体,该中间体和O₂反应,生成了超氧负离子（O₂·^-）,随后与水中H⁺反应生成了H₂O₂.     

腐殖质及其模型化合物的H2O2光化学生成研究

在模拟太阳光下研究了多种腐殖质及其模型化合物的过氧化氢（H₂O₂）生成动力学,并对其生成机制进行了探讨.结果表明不同来源或不同形式的腐殖质在模拟太阳光照射下均能产生H₂O₂.不同腐殖质生成H₂O₂速率差异不大,范围为6.379~15.784nmol/（L·min）,腐殖酸生成H₂O₂速率略快于富里酸.对于腐殖质模型化合物,邻苯二酚、间苯二酚、对苯二酚、苯醌、邻茴香胺、对茴香胺、水杨酸和2,6-二甲氧基-1,4-苯醌等8种模型化合物没有产生明显的H₂O₂,而藜芦醇、对氨基苯甲酸、3,5-二羟基苯甲酸（DHBA）、2,5-二羟基-1,4-苯醌、苯酚、苯甲酸和苯胺等7种化合物均可检测到H₂O₂产生.但其产生H₂O₂的速率差异较大,相差1~2个数量级,生成H₂O₂速率最快的化合物为2,5-二羟基-1,4-苯醌和DHBA,较慢的为苯酚、苯甲酸和对氨基苯甲酸.基于腐殖质生成H₂O₂机制,推测典型模型化合物DHBA的H₂O₂生成机制可能为光照条件下该化合物跃迁为单重激发态,该激发态发生分子内电子转移,生成还原性自由基中间体,该中间体和O₂反应,生成了超氧负离子（O₂·^-）,随后与水中H⁺反应生成了H₂O₂.     

胡敏酸对不同矿物结合汞的还原作用

采用扩散吸收法探讨了胡敏酸对不同矿物结合态汞的还原作用及光照的影响.结果表明:两种胡敏酸(TJ和SH)对碳酸钙、氧化锰和赤铁矿结合态汞均具有明显的还原作用,还原动力学过程表现为先递增后渐趋平稳,可用双常数方程、Elovich方程和指数方程拟合;还原容量与吸持矿物类型有关,平均还原率大小为:CaCO3-Hg(0.67%)>Fe2O3-Hg(0.42%)>MnO2-Hg(0.19%);光照对胡敏酸还原矿物结合态汞具有强化效应,以CaCO3-Hg和Fe2O3-Hg光强化效果最明显,平均还原率较遮光时高出0.10%以上;两种胡敏酸(SH和TJ)对矿物结合态汞的还原能力存在差异(P<0.1),遮光条件下SH的还原能力均高于TJ,而光照条件下TJ对CaCO3-Hg的还原能力大于SH,对MnO2-Hg的还原则无显著差异,意味着SH的光敏性低于TJ,可能与不同胡敏酸氧化还原活性基团含量和芳香化程度(E4/E6)不同有关.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well. Translated from Acta Scientiae Circumstantiae, 2005, 25(6): 816–820 [译自: 环境科学学报]     

翻堆对好氧堆肥腐殖质电子转移能力的影响

开展了连续通风和翻堆两种典型的通风方式进行污泥好氧堆肥,通过分析堆肥腐殖质中富里酸(FA)和胡敏酸(HA)的光谱特征以及本底/化学还原容量(NRC/CRC)的时态变化,研究其对污泥好氧堆肥过程中富里酸(FA)和胡敏酸(HA)的形成和电子转移能力(ETCs)的影响.结果表明:与翻堆处理相比,连续通风处理促进了堆肥FA和HA中类蛋白质组分的减少和类腐殖质组分的增加,强化了高温期和腐熟期FA的电子转移能力(CRC分别增加了176.55和123.24μmol e^-/gC),但降低了HA和升温期FA的电子转移能力(CRC分别降低了246.47和116.13μmol e-/gC).相关性分析表明,影响污泥堆肥腐殖质电子转移能力的主要因素为pH值、SUVA₂₅₄、SUVA₂₉₀和类蛋白质组分,翻堆处理促进了类腐殖质组分对腐殖质电子转移能力的影响.     

生活垃圾堆肥过程中腐殖质及有机态氮组分的变化

利用实际城市生活垃圾,采用工厂化工艺进行堆肥试验,探讨在堆肥过程中腐殖质及有机态氮组分的动态变化.结果表明,随着堆肥的进行,有机碳、富里酸、全氮、酸水解性有机氮含量均有不同程度的降低,与堆肥前相比,降低幅度分别为53.00%、64.73%、21.78%、22.80%.而腐殖质、胡敏酸、氨基酸态氮则分别在堆肥的第35d达到最低点,而后呈逐渐增加的趋势.酰胺态氮、氨基糖态氮在堆肥的第21d达到最高峰.堆肥过程中,腐殖质与胡敏酸、酸水解有机态氮与全氮含量显著相关.胡敏酸的红外光谱分析结果表明,堆肥后胡敏酸分子的芳构化程度明显增强.     

Evaluation of oxidation stability of lignite humic substances by DSC induction period measurement

The stability of lignite humic acids and four regenerated humic acids was estimated by employing differential scanning calorimetry. Induction period for the oxidative decomposition of humic matter was calculated from non-isothermal measurements at six different rates of heating. To simulate the gradual evolution history of humic acids, different intensities of oxidation attack by nitric acid on the original lignite was used. Experimental data showed higher stability of natural humic acids in the temperature range where the decomposition step occurred. On the other hand, extrapolation to lower temperatures and calculated kinetic parameters did not correspond to the order observed at higher temperatures. An oscillating trend of calculated parameters of the two proposed parts of stability was observed, which agreed with data concerning regenerated humic acids production. The approach applied in this work represents a rapid and useful method for evaluation of organic matter stability.     

Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

The sorption and desorption behaviors of two perfluoroalkane sulfonates（PFSAs）, including perfluorohexane sulfonate（PFHx S） and perfluorooctane sulfonate（PFOS） on two humic acids（HAs） and humin（HM）, which were extracted from a peat soil, were investigated. The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances（HSs） was much higher than PFHx S. For the same PFSA compound, the sorption on HSs followed the order of HM 〉 HA2 〉 HA1. These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs. The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity, but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs. Compared to PFOS,PFHx S displayed distinct desorption hysteresis, probably due to irreversible pore deformation after sorption of PFHx S. The sorption of the two PFSAs on HSs decreased with an increase in p H in the solution. This is ascribed to the electrostatic interaction and hydrogen bonding at lower p H. Hydrophobic interaction might also be stronger at lower p H due to the aggregation of HSs.     

腐殖质对污泥厌氧消化的影响及其屏蔽方法

《巴黎气候协定》的签署意味着污水处理碳中和运行时代的来临,这就需要将剩余污泥尽可能最大程度地转化为可再生能源—甲烷(CH4).细胞破壁、木质纤维素破稳及腐殖质解抑制是提高污泥厌氧消化能源转化率的主要技术手段.相对于细胞与木质纤维素,腐殖质不仅结构更为复杂、自身难以生物降解,而且还会抑制其它有机物水解.虽然腐殖质亦有促进酸化、产氢/乙酸、产甲烷过程的微弱可能,但它对水解过程的抑制是肯定的、显著的、难以逆转的.因此,需要深入了解污泥中腐殖质来源、形成、结构及性质,综合分析它对污泥厌氧消化水解、酸化、产氢/乙酸、产甲烷阶段的各种影响,探讨消除腐殖质抑制水解过程的不同技术路径,重点描述外加金属离子对腐殖质的屏蔽作用.以期为提高污泥厌氧消化能源转化率制定可行的技术路线.