凹凸棒土对腐殖酸的低温吸附性能研究

首次研究凹凸棒土对饮用水中腐殖酸的低温吸附性能,考察5℃条件下,吸附时间与腐殖酸初始浓度、吸附剂投加量、pH对凹凸棒土吸附腐殖酸的影响,确定吸附剂的吸附等温线、吸附动力学和热力学等相关理论参数,研究凹凸棒土对腐殖酸的吸附性能与机理。结果表明,江苏盱眙凹凸棒土在温度5℃、pH=4、水中腐殖酸初始浓度为5 mg/L,投加量为15 g/L的条件下,吸附180 min后对腐殖酸的去除率可达97.26%。凹凸棒土对腐殖酸的吸附符合二级吸附动力学方程与Freundlich吸附等温式,吸附过程由孔隙内扩散过程控制,吸附为自发的吸热过程,包括物理吸附与化学吸附。根据Fre-undlich吸附等温式拟合计算,5℃、pH=7时理论最大吸附量为9 mg/g,说明凹凸棒土对于低温饮用水中腐殖酸具有良好的吸附效果。     

Removal of low concentrations of ammonium and humic acid from simulated groundwater by Vermiculite/Palygorskite mixture

Contaminants in water are classified into different types based on their physical and chemical properties. Thus, more than one type of sorbents may be needed for their removal. In this article, a combination of vermiculite with palygorskite was studied for their simultaneous removal of ammonium and humic acid from simulated groundwater. Batch results showed that the Langmuir model described ammonium adsorption well with an adsorption capacity of 22 mg/g while the humic acid adsorption data fitted to the linear adsorption better, suggesting different removal mechanisms of these two types of contaminants. Kinetic studies showed an instantaneous removal of ammonium and humic acid. A column packed with mixture of equal volumes of vermiculite and palygorskite could treat 100 pore volumes for ammonium removal at an initial concentration of 10 mg/L and 500 pore volumes for humic acid removal at an initial concentration of 20 mg/L before the effluent concentrations exceeded the standard.     

Surface charge and adsorption from water onto quartz sand of humic acid

The surface charge of humic acid under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)) was determined by a titration method using a cationic polyelectrolyte as titrant. Adsorption isotherms in batch experiments of the polymer from water onto quartz sand were determined at 20 degrees C, 40 degrees C, and 60 degrees C and under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)). The data indicate significant decrease of humic acid surface charge by decreasing the pH value from 10.0 to 4.1. Similar decrease of humic acid surface charge was observed by increasing either the ionic strength or the affinity of the divalent cation toward the humic acid. At ambient temperature the adsorption of humic acid on the quartz sand seems to be controlled mainly by electrical interaction between the organic particle and the solid substrate. A correlation is found between the surface charge and the adsorbed amount of the polymer, the adsorbed amount increases when the surface charge of humic acid decreases. The increase of the adsorbed amount with the temperature suggests that adsorption process is endothermic.     

Influence of pH and ozone dose on the content and structure of haloacetic acid precursors in groundwater

This study investigated the effects of pH (6-10) and ozone dose [0.4-3.0?mg O(3)/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85?±?0.18?mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65?% fulvic and 14?% humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309?±?15?μg/L). Ozonation at pH?6-10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65-90?% achieved using 3.0?mg O(3)/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH?10 (up to 68?% HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1?±?6.0?μg/mg DOC in raw water to 152?±?8?μg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH?10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.     

Kinetics and mechanisms of interaction of simazine with humic acids

Abstract

The adsorption of simazine on two fractions of hu‐mic acids of different molecular size was investigated at a pH range of 2.5 to 6.2. The amounts of the herbicide adsorbed decreased with increasing pH for both of the two humic acids fractions used and no adsorption was observed at pH 5.5. The adsorption capacity of fraction I (M_v >100,000) exceeded that of fraction IV (M_v < 4,000) over the entire pH region used. No appreciable changes in the adsorbed amounts were observed after 24 hours.

Continuous flow dialysis techniques were used to determine the extent of binding between simazine and dissolved humic acids. It was observed that 50% and 60% of simazine added were thus removed from the dialysis bags containing humic acids fractions I and IV,respectively. Higher amounts of simazine were adsorbed by the high molecular weight humic fraction. The adsorption processes involve ionic bonds between simazine and humic acids. In addition it is likely that hydrogen bonds and physical forces are also involved in the adsorption of simazine by humic acids.     

不同工艺对含高浓度腐殖酸地下水处理的可行性

针对内蒙古农村地区高腐殖酸地下水的处理问题,分别对（pH调节）-PAC强化混凝、高锰酸钾预氧化／混凝、活性炭吸附／混凝、Fenton氧化等技术处理的可行性进行了研究,同时利用三维荧光和高效体积排阻色谱分析处理前后水中有机物的组成变化特征。有机分析结果显示,水中的有机物为腐殖酸类物质,分子量分别为1600和3500,腐殖酸类物质为水中色度的主要贡献者。原水PAC强化混凝、高锰酸钾预氧化／PAC混凝对有机物的去除效果不佳,处理前后水样DOC浓度无明显变化,而pH调节．PAC强化混凝、微米活性炭吸附和Fenton氧化均能有效去除有机物。将原水pH调节至6．5,经300mg／LPAC混凝后出水DOC降至5．99mg／L。活性炭投加量为0．6g／L时,DOC降至7．6mg／L,然后采用60mg／LPAC混凝出去高度分散而不易沉降的小颗粒活性炭。此外,当反应初始pH值为3,过氧化氢投加量为0．5％（v／v）,亚铁和双氧水摩尔比为0．05时,出水DOC降至5．6mg／L,氧化后有小分子有机物生成。     

Effect of humic acid on water chemistry, bioavailability and toxicity of aluminium in the freshwater snail, Lymnaea stagnalis, at neutral pH

The influence of humic acid on the water chemistry of environmentally relevant concentrations of Al at neutral pH was studied, together with its effect on the bioavailability and toxicity of Al in Lymnaea stagnalis. Humic acid significantly reduced the loss of Al from the water and increased the fraction of filterable Al, although this was a relatively small fraction of total Al. Filterable Al concentration in the presence or absence of humic acid was independent of initial Al concentration. Humic acid only partly reduced toxicity, as observed by a reduction in behavioural suppression, and had no effect on the level of Al accumulated in tissues. These results suggest that humic acid maintains Al in a colloidal form that is bioavailable to L. stagnalis. However, these colloidal Al-humic acid species were less toxic since behavioural toxicity was reduced. Humic acid may play an important role in limiting the toxicity of Al to freshwater organisms.     

Fractionation of heavy metals and distribution of organic carbon in two contaminated soils amended with humic acids

The effects of humic acids (HAs) extracted from two different organic materials on the distribution of heavy metals and on organic-C mineralisation in two contaminated soils were studied in incubation experiments. Humic acids isolated from a mature compost (HAC) and a commercial Spaghnum peat (HAP) were added to an acid soil (pH 3.4; 966 mg kg(-1) Zn and 9,229 mg kg(-1) Pb as main contaminants) and to a calcareous soil (pH 7.7; 2,602 mg kg(-1) Zn and 1,572 mg kg(-1) Pb as main contaminants) at a rate of 1.1g organic-C added per 100g soil. The mineralisation of organic-C was determined by the CO(2) released during the experiment. After 2, 8 and 28 weeks of incubation the heavy metals of the soils were fractionated by a sequential extraction procedure. After 28 weeks of incubation, the mineralisation of the organic-C added was rather low in the soils studied (<8% of TOC in the acid soil; <10% of TOC in the calcareous soil). Both humic acids caused significant Zn and Pb immobilisation (increased proportion of the residual fraction, extractable only with aqua regia) in the acid soil, while Cu and Fe were slightly mobilised (increased concentrations extractable with 0.1M CaCl(2) and/or 0.5M NaOH). In the calcareous soil there were lesser effects, and at the end of the experiment only the fraction mainly related to carbonates (EDTA-extractable) was significantly increased for Zn and decreased for Fe in the humic acids treated samples. However, HA-metal interactions provoked the flocculation of these substances, as suggested by the association of the humic acids with the sand fraction of the soil. These results indicate that humic acid-rich materials can be useful amendments for soil remediation involving stabilisation, although a concomitant slight mobilisation of Zn, Pb and Cu can be provoked in acid soils.     

Removal of organic polyelectrolytes and their metal complexes by adsorption onto xonotlite

Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed by adsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were approximately 80% and 30%, respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially, indicating that adsorption efficiency depends on the number of functional groups of humic substances. Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanning electron microscopy. The calculated heat of adsorption was of 330 kJ mol(-1) which was evaluated from the Clapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can be easily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to their precipitation.     

回灌型准好氧填埋场脱氮特性及加速稳定化研究

采用2个模拟填埋生物反应器,1号柱渗滤液简单回灌,2号柱为渗滤液回灌准好氧联合运行方式,研究了渗滤液回灌准好氧生物反应器填埋场的脱氮特性及加速垃圾稳定化特性.研究结果表明:渗滤液回灌准好氧填埋场具有很强的脱氮能力,2号柱由厌氧运行方式改为准好氧条件下,渗滤液中的氨氮和凯式氮浓度分别由最大值的3 198 mg/L和3 345 mg/L降低到第160 d的73 mg/L和81 mg/L,去除率分别为97.7%和97.6%,pH快速升高到8.0左右,COD浓度快速降低.渗滤液中溶解性有机物(DOM)分级结果表明,2号柱HA和FA含量的增加明显快于1号柱.2号柱DOM的三维荧光光谱特性发生了较大变化,荧光基团从60 d结构简单的类蛋白物质转变为95 d结构复杂的类胡敏酸和富里酸物质,而l号柱渗滤液DOM荧光基团一直是结构简单的类蛋白物质.结果表明回灌准好氧生物反应器填埋场的稳定化速度远快于简单回灌的生物反应器填埋场.     

矿物复合PAC混凝去除给水中腐殖酸的研究

为了降低饮用水中有机微污染物的浓度,对矿物高岭土复配聚合氯化铝（PAC）吸附混凝共沉降去除腐殖酸进行了研究,结果表明：矿物高岭土与PAC复配的最佳量均为12 mg/L,此时水样浊度、腐殖酸去除率分别达到98.9%和97.9%,出水残余铝浓度0.16 mg/L。高岭土复配对于处理后水中铝形态也产生了影响,与单独使用PAC相比,总铝浓度降低了24%,特别是对人体毒害较强的溶解态铝浓度降低了71%。     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

Competition between alga (Pseudokirchneriella subcapitata), humic substances and EDTA for Cd and Zn control in the algal assay procedure (AAP) medium

The chemical speciation of trace metals in natural waters has important implications for their biogeochemical behavior. Trace metals are present in natural waters as dissolved species and associated with colloids and particles. The complexation of one trace metal (Cd and Zn at 200 and 390 microg/l respectively) with a green alga Pseudokirchneriella subcapitata in colloid-free algal culture medium and in presence of colloidal humic substances (HS) is presented. The influence of the nature of colloids was also addressed using three "standard" HS: fulvic acid (FA) and, soil (SHA) and peat humic acids (PHA). The chemical speciation model, MINTEQA2, was used to simulate the influence of pH and standardized culture medium on metal association with humic substances. The model was successfully modified to consider the differences in the metal complexation with fulvic (FA) and humic acids (HA). The deviations of concentrations of metals associated with HS between experimental results and model predictions were within a factor of approximately 2. The results of speciation model highlight the influence of the experimental conditions (pH, EDTA) used for alga bioassay on the behavior of Cd and Zn. The computed speciation suggests working with a pH buffered/EDTA-free mixture to avoid undesirable competition effects. The behavior of Cd and Zn in solution is more strongly influenced by HS than by alga. Metal-HS associations depend on metal and humic substance nature and concentration. Cd is complexed to a higher extent than Zn, in particular at larger HS concentration, and the complexation strength is in the order FA相似文献   

Influence of suspended clay minerals and humic matter on the solid phase extraction efficiency of selected pesticides from water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and alpha-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was > or =0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.     

Kinetics of disaggregation of humic acid in water

The extent of disaggregation of humic acid particles in water was measured as a function of time, initial concentration, pH of the suspension and the temperature. In all experiments the amount of humic acid particles disaggregated was characterized by the corresponding fraction of the suspension, which was able to pass a 0.01 μm membrane filter.It was found that the amount disaggregated after 1000 hours was proportional to the initial concentration of the humic acid particles in the aqueous suspension and increased considerably with the temperature. Decreasing the pH of the suspension from about 6 to zero caused the extent of disaggregation also to decrease continuously.The kinetic measurements revealed that about 3% of the humic acid are disaggregated within 25 hours, 4% within 200 hours and 5% within 1500 hours at a pH around 4. The rates of disaggregation were found to be proportional to the initial concentration of the particles and increased considerably with the temperature.     

Influence of Suspended Clay Minerals and Humic Matter on the Solid Phase Extraction Efficiency of Selected Pesticides from Water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and α-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was ≥0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.     

Role of cupric ions in the H2O2/UV oxidation of humic acids

The purpose of this study is to reveal the role of cupric ions as a natural water contaminant in the H2O2/UV oxidation of humic acids. Humic acids are naturally occurring organic matter and exhibit a strong tendency of complexation with some transition metal ions. Chlorination of humic acids causes potential health hazards due to formation of trihalomethane (THM). The removal of THM precursors has become an issue of public concern. The H2O2/UV process is capable of mineralizing humic acids due to formation of a strong oxidant, hydroxyl radicals, in reaction solution. Experiments were conducted in a re-circulated photoreactor. Different cupric concentrations (0-3.8 mg/l) and different pH values (4-9) were controlled to determine their effects on the degradation of humic acids, UV light absorbance at 254 nm, and H2O2. The presence of cupric ions inhibits humic mineralization and decreases the rate of destruction of humic acids which absorb UV light at 254 nm. On the other hand, the higher the cupric concentration, the lower the H2O2 decomposition rate. In the studied pH range, the minimum of total organic carbon (TOC) removal occurs at pH = 6 in the presence of 2.6 mg/l of cupric ions; both acidification (pH = 4) and alkaline condition (pH = 9) lead to a better removal of TOC. It is inferred from this study that the cupric-complexed form of humic acids is more refractory than the non-complexed one.     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.     

TiO2/EP光催化降解水体中微污染磺胺嘧啶的研究

制备了膨胀珍珠岩（EP）为载体的TiO2催化剂（TiO2/EP）,对使用较为广泛的抗生素磺胺嘧啶（SDZ）进行了光催化降解研究,探讨了TiO2的负载量、溶液的初始浓度、初始pH、无机离子（HCO3^-、SO4^2-和Cl^-）和腐殖酸（HA）对SDZ降解效果的影响。结果表明：SDZ的光催化降解符合一级反应动力学方程;当TiO2最佳负载量为20 wt%,SDZ浓度为5 mg/L,pH=6.7,紫外光照射强度为1 000μW/cm^2,反应时间为45 min时,SDZ的降解率达到96%;HCO3^-在低浓度时能促进SDZ的光催化降解,高浓度时促进作用不明显;SO4^2-和Cl^-对SDZ的光催化降解有轻微的抑制作用;HA对SDZ光催化降解有显著的抑制作用,浓度越高,抑制作用越强。UV-TiO2/EP是一种去除水体中微污染SDZ的有效方法。     

Organic matter source discrimination by humic acid characterization: Synchronous scan fluorescence spectroscopy and Ferrate(VI)

In this study, seven soil and sedimentary humic acid samples were analyzed by synchronous scan fluorescence (SSF) spectroscopy. The spectra of these humic acids were compared to each other and characterized, based on three major SSF peaks centered at approximately 281, 367 and 470 nm. Intensity ratios were calculated based on these peaks that were used to numerically assist in source discrimination. All humic acid samples were then reacted with Ferrate(VI) and were again analyzed with SSF. Upon the addition of Ferrate(VI) SSF spectra were obtained which more readily differentiated humic acid source. This method will assist geochemists and water management districts in tracing sources of organic matter to receiving water bodies and may aid in the elucidation of the chemical nature of humic acids.