Effects of Ozonation on Natural Organic Matter Reactivity in Adsorption and Biodegradation Processes – A Case Study: The Úzquiza Reservoir Water

In this paper the influences of preozonation on the effectiveness of NOM adsorption and biodegradation processes are studied. Three different types of water have been used in this study: A natural water from the Úzquiza Reservoir (Burgos, Spain), synthetics waters prepared using natural humic substances (fulvic and humic acids extracted from the Úzquiza Reservoir) and a synthetic water prepared using a commercially supplied humic acid. The effect of preozonation on NOM adsorption by activated carbon is evaluated: adsorption of humic acids (hydrophobic, high molecular weight compounds) is improved following preozonation; however, for the fulvic acids (hydrophilic, low molecular weight compounds), no net appreciable effect of preozonation on adsorption was observed. Preozonation increases the biodegradability of NOM: biodegradable dissolved organic carbon (BDOC), which was determined using two different bioassays (Billen-Servais method and Joret-Lévi method), increases with increasing ozone dosage. A characterization of humic substances based on their adsorption and biodegradability properties is also reported, showing the effect of ozone.     

Contribution of Ozone to the Removal of Organic Materials in a Process Including a slow Filtation Through sand and Activated Carbon

The experiments were conducted on full scale at the Mont-Valérien treatment plant treating the Seine river downstream from Paris. Over one year, the efficiency of different types of full-scale slow filters (sand, sand +granular activated carbon (GAC), with and without preozonation) and pilot scale rapid GAC filters with preozonation were compared. Slow sand filter remove an average of 10% TOC primarily through biodegradation. Slow GAC remove an addi-tionnal 15% TOC primarily through adsorption. The total reduction is thus 25%. Ozone removes 5% but does not enhance GAC performance.     

Effect of Ozone Dosage for Removal of Model Compounds by Ozone/GAC Treatment

This research employed batch ozonation and GAC (granular activated carbon) column to investigate the effect of preozonation dosage on the subsequent GAC adsorption, in terms of the adsorption capabilities for small and large molecules.

For large target compounds like humic acid, the adsorption efficiency was improved with higher ozone dosages, whereas the combined effect of ozonation coupling with GAC for small model compounds seems to be negative. In addition, there is a selective adsorption between the chlorinated disinfection by-product (DBP) precursors and other non-precursors, and most of the non-precursors are less adsorbable than the precursors.     

Systematic Approach to Quantify Adsorption and Biodegradation Capacities on Biological Activated Carbon Following Ozonation

The goal of this research was to develop a systematic approach to quantify adsorption and biodegradation capacities on biological activated carbon (BAC). The role of absorption and biodegradation on BAC was studied using a continuous column. Several media, i.e., granular activated carbon (GAC), seeded glass bead and seeded GAC, and a target compound (p-hydroxybenzoic acid) were selected. Before breakthrough, the effluent of the GAC column contained a small amount of p-hydroxybenzoic acid that contributed the greatest amount of organic carbon to the effluent of the glass bead column, which suggests that adsorption should be the prevailing mechanism for removal the p-hydroxybenzoic acid, and biodegradation should be responsible for reducing the ozonation intermediates. Also, the bioactivity approach (biomass respiration potential, BRP) of BAC can not only reveal the importance of biodegradation mechanisms for the intermediates of ozonation, but also quantify the extent of the adsorption or biodegradation reaction occurring on BAC.     

磺胺嘧啶在颗粒活性炭和碳纳米管上的吸附特性

近年来,水环境中抗生素的去除成为关注热点。研究讨论了磺胺嘧啶在颗粒活性炭(GAC)和多壁碳纳米管(MWCNT)上的吸附特性,并考察了pH、离子强度和腐殖酸等因素对吸附的影响。结果表明,pH对吸附效果有着显著的影响;腐殖酸的存在与磺胺嘧啶形成了竞争吸附;离子强度的变化对吸附效果没有很大影响。     

Influence of Preozonation on the Formation of Chlorination Disinfection By-products – A Case Study: The Úzquiza Reservoir Water

The influence of preozonation on the formation of chlorination disinfection by-products (DBPs) is studied for three different types of water: a natural water from the Úzquiza Reservoir (Burgos, Spain), synthetics waters prepared using natural fulvic and humic acids extracted from the Úzquiza Reservoir and a synthetic water prepared using a commercially supplied humic acid. The main factors intervening in this process have been reviewed: the delay time between ozonation and chlorination, the ozone reaction pathway, the type of NOM, the applied ozone dose and the presence of bromide ion. Preozonation decreases trihalomethane formation potential (THMFP) for both humic and fulvic acids, being this effect more significant for the humic acids. The molecular pathway of ozone seems to be more selective than the radical pathway for THMFP removal from humic acids. Ion bromide content of the raw water greatly influences the effect of preozonation on THMFP. The influence of preozonation on the formation of some minority DBPs has been studied too.     

A comparison between catalytic ozonation and activated carbon adsorption/ozone-regeneration processes for wastewater treatment

Two methods based on the use of granular activated carbon (GAC) and ozone to remove organic compounds from water have been investigated. Both methods have been applied to degrade an aqueous solution of gallic acid and a secondary effluent from a wastewater treatment plant (WWTP). One of the methods, namely catalytic ozonation, implies simultaneous ozonation and adsorption onto GAC. This process takes advantage of the oxidizing power of ozone and the adsorption capacity of GAC but also of the catalytic transformation of ozone into secondary oxidants on the GAC surface. The efficiency of catalytic ozonation was compared to those of single adsorption and single ozonation. It was found that the catalytic process highly improves the conversion of total organic carbon (TOC) and makes a more efficient use of ozone than the single ozonation process. To illustrate the reusability of the catalyst, the GAC was reused four times through a series of consecutive experiments. No loss of catalytic activity was observed when treating the WWTP effluent but some deactivation could be appreciated when treating the aqueous solution of gallic acid. This deactivation could be attributed to some porosity destruction and surface oxidation produced as a result of reactions of aqueous ozone on the GAC surface. The other method investigated is an adsorption-regeneration process (namely GAC/O₃-regeneration) that comprises two steps: dynamic adsorption onto GAC and further regeneration of the spent GAC with gaseous ozone. The adsorption stage of the GAC/O₃-regeneration experiments was carried out in a continuous flow adsorption column and breakthrough curves were obtained. It was observed that the GAC used in this work adsorbed gallic acid very efficiently but exhibited limited capacity to remove chemical oxygen demand (COD) from the WWTP effluent. The optimum ozone dose to regenerate the spent GAC after gallic acid adsorption was found to be about 0.4 g O₃/g GAC, with results showing around 90% regeneration efficiency. As a result of incomplete regeneration, the GAC adsorption capacity progressively decreased with the number of adsorption–regeneration cycles. The GAC/O₃-regeneration method was not successful at treating the WWTP effluent as low adsorption uptake was observed. Moreover, the GAC became damaged after regeneration because of excessive oxidation of its surface.     

Effects of Ozonation on Molecular Weight Distribution of Humic Substances and Coagulation Processes – A Case Study: The Úzquiza Reservoir Water

In this article the influence of preozonation on the effectiveness of NOM removal via coagulation processes will be studied (focusing on the influence of the calcium hardness) as well as changes in MW (molecular weight) distribution of humic substances caused by ozonation. Additionally, THMFP removal in both ozonation and preozonation-coagulation processes is assessed. Three different types of water have been used in this study: a natural water from the Úzquiza Reservoir (Burgos, Spain), a synthetic water prepared using natural fulvic acids extracted from the Úzquiza Reservoir and a synthetic water prepared using a commercially supplied humic acid. Molecular weights of humic substances were determined using high-performance size exclusion chromatography (HPSEC); average molecular weights calculated for the unozonated humic substances are 4500 Da for the commercial humic acids and 1000 Da for the natural fulvic acids extracted from the Úzquiza Reservoir. Preozonation shifted the molecular weight distribution of humic substances (both humic and fulvic acids) towards lower average molecular weight values. For the natural water from the Úzquiza Reservoir (with low levels of calcium hardness and hydrophobic fraction (humic substances) being the main fraction of NOM), preozonation has a negative effect on the effectiveness of the coagulation process for NOM removal: the percentages of TOC removal via coagulation decrease with increasing ozone dosage; the maximum TOC removal (33%) is achieved for the unozonated water. Also for this water, ozonation reduced 5–25% of THMFP with ozone doses varying from 0.25 to 2.5 mg O₃/L. A preferential THMFP removal, that is to say, higher reduction in THMFP (43%) relative to TOC (28%) is achieved by the coagulation-flocculation process; this also occurs when preozonation is used, independently of ozone dosage.     

腐植酸在土壤中对Cu~(2+)的吸附特性影响

研究了腐植酸对Cu2+在土壤上吸附特性以及相关因素的影响。结果表明,在等温吸附实验中,无论是否加入腐植酸,Cu2+的吸附都能够较好地符合Freundlich方程;并且Cu2+在供试土样上的吸附量随温度升高而降低,表明吸附为放热过程。在吸附动力学实验中,不加腐植酸时,Cu2+在供试土样上的吸附动力学最优方程为Elovich方程,加入腐植酸溶液后,吸附动力学最优方程为一级动力学方程,且Cu2+的吸附平衡时间明显缩短。随着加入腐植酸量的增加,土壤样品对Cu2+的吸附量明显增加。     

原水深度处理过程中的生物稳定性和分子量分布

研究了水源水在"预臭氧+常规+主臭氧/生物活性炭"深度处理工艺流程净化中的各工艺段出水有机物及分子量的变化特征,建立了生物稳定性与有机物分子量的关系,实现了对深度处理后供水水质生物稳定性的评估。研究结果表明:预臭氧可将大分子的天然有机物分解为相对分子质量小于1000的有机物,并提高水的可生化性;导致常规处理工艺去除水中有机物的效率降低;主臭氧可将有机物进一步氧化,并将部分氧化成相对分子质量小于500的有机物;生物活性炭可提高出水的生物稳定性,但对相对分子质量小于1000的有机物去除有限;分子量越小生物稳定性越差,越不容易被去除。此研究结果为评估水源水质深度处理的生物稳定性提供了理论依据。     

Enhanced removal of humic acid from water by micelle-montmorillonite composites: Comparison to granulated activated carbon

Removal of humic acid (HA) from water by octadecyltrimethyl-ammonium (ODTMA) micelle–montmorillonite (MMT) composites and by granulated activated carbon (GAC) was studied in dispersion and by filtration. FTIR measurements emphasized that the ODTMA micelle–clay-mineral composite differs from the ODTMA monomer-clay-mineral one. HA adsorption by GAC in dispersion was moderately reduced from 100% initially to 75% with an increase in HA concentrations. In contrast, the fractions adsorbed by the composite increased monotonically with HA concentrations from very low adsorption up to 80%. This effect was explained by the presence of a small concentration of ODTMA monomers in dispersion, which adsorbed on the negatively charged HA and partially neutralized it, or caused charge reversal, which in turn inhibited HA adsorption by the positively charged composite. This effect was verified by mobility measurements and was found to be more pronounced at low HA concentrations. This trend of increase in HA removal with an increase in HA concentration (3 and 10 ppm) was also observed in filtration (50% and 85% removal, respectively), when employing columns of the composite mixed with sand (to improve flow). Throughout the experiment the removal of high HA concentration (10 ppm) by the composite filter remained ~ 80% whereas, the removal by the GAC filter decreased from an initial 80% removal to a complete recovery of the HA (no removal) after the passage of 20 L (200 pore volumes). Upon applying sand of higher quality in the columns the removal of low HA concentrations was nearly complete by the composite column while the GAC only slightly contributed to its removal (for a passage of 100 L (1000 pore volumes)).     

Removal of Humic Acid Using PEI‐Modified Fungal Biomass

Abstract

A modified fungal biomass was prepared through the adsorption of polyethylenimine (PEI) and subsequent crosslinking with glutaraldehyde on the biomass surface. FTIR result verified that the amine groups were introduced on the biomass surface. As a large number of amine groups are present on the biomass surface and can be protonated in solution, the modified biomass was positively charged at pH<10.3. The modified biomass was used as an adsorbent to remove humic acid in a series of batch adsorption experiments. The amount of humic acid adsorbed on the biosorbent decreased with increasing solution pH, and the electrostatic interaction between the positive protonated amine groups on the biomass surface and the negative carboxyl groups in the humic acid molecules played an important role in humic acid adsorption. The time‐dependent sorption of humic acid on the biomass can be described well by the Fickian diffusion model at the initial stage and the pseudo‐second‐order equation over 10 h. Using the Langmuir adsorption isotherm, the maximum sorption capacity of the modified biomass for humic acid at pH 5 was 96.5 mg/g. The desorption experiments showed that the humic acid loaded biomass could be easily regenerated in a 0.1 M NaOH solution, and the regenerated biomass possessed good adsorption capacity up to the fifth cycle. The PEI‐modified biomass with polyamine chains shows the potential for application in water treatment for the removal of humic substances.     

Preozonation of Chlorophenolic Wastewater for Subsequent Biological Treatment

Preozonation was investigated for its effects on the biodegradability of five chlorophenolic compounds in activated-sludge systems. The biodegradability was expressed in terms of the oxidation of each compound itself and of the total organic contents of the whole sample.

Results indicate that preozonation could either promote or retard the biodegradability, depending primarily on whether or not the sludge used in the subsequent biological system had been acclimated beforehand. For unacclimated sludge, preozonation was found to be helpful in promoting the biodegradability of all the compounds, especially the chlorophenols with a meta-position chlorine attachment. For acclimated sludge, a reverse effect generally, was observed.     

Purification of Polluted Source Water with Ozonoation and Biological Activated Carbon

In order to determine effective processes for purifying polluted source waters 1n Harbin City, various processes consisting of ozonation, sand filtration, and/or GAC filtration and adsorption, i.e., ozonation ( “O₃” Process), ozonatlon/sand filtration ( “O₃ + SF” Process), ozonation/biological activated carbon ( “O₃ + BAC” Process), ozonation/sand filtration/biological activated carbon ( “O₃ + SF + BAC” Process), and granular activated carbon (“GAC” Process) were tested In an 8 m³/d capacity pilot plant. In addition, a small plant of 500 L/d capacity was used to conduct comparative studies between the two processes “GAC” and “O₃ + BAC”, as well as two types of carbon.     

Performance of Granular Activated Carbon (GAC) Adsorption and Biofiltration in the Treatment of Biologically Treated Sewage Effluent

Abstract

In this study, the performance of GAC adsorption and biofiltration systems in treating biological treated sewage effluent (BTSE) was evaluated in terms of organic removal efficiency, organic fractions, and molecular weight distribution (MW) of organic matter (OM) removed. The GAC biofilter removed 23.5% and 61% of the hydrophobic fractions and hydrophilic fractions of OM in the BTSE respectively. MW distribution studies of GAC filter and GAC adsorption revealed the following: Hydrophobic fraction of the effluent showed a peak at 345 dalton after GAC biofiltration and 256 dalton after GAC adsorption, whereas, with hydrophilic fractions, peaks at 46,178 and 345 daltons were observed after GAC biofiltration and peaks at 46,178 and 256 daltons after GAC adsorption. Transphilic fraction showed the peaks at 12,783 dalton with GAC biofiltration, and 1,463 dalton with GAC adsorption. The performance of the GAC biofilter was successfully mathematically modelled.     

Evaluation of adsorption and coagulation characteristics of humic acids preceded by alternative advanced oxidation techniques

Humic substances mainly humic acids constitute the major fraction of natural organic matter in water supplies. Humics express diverse actions primarily related to the formation of potentially harmful disinfection by products (DBPs). Therefore, the removal of DBP precursors through numerous treatment techniques gains high importance. Besides the conventional treatment processes, the applications of advanced oxidation techniques are considered as effective tools for the elimination of humic acids (HAs) from natural waters. In the present study, both the adsorption and coagulation characteristics of humic acid samples are evaluated subsequent to pretreatment by photocatalytic oxidation and ozonation. The changes in preoxidized humic acid solutions are assessed in relation to the alterations induced in the UV-vis and fluorescence spectroscopic properties. The removal efficiency of color in terms of Color₄₃₆ and aromaticity with respect to UV₂₅₄ are presented relevant to each treatment step. Major key parameters such as the selection of coagulant types (alum and ferric chloride), coagulant aids (ionic and non-ionic polyelectrolyte) and optimum coagulant dose were comparatively discussed. The adsorption characteristics of powdered activated carbon (PAC) and granular activated carbon (GAC) were investigated.     

活性炭多维电极法去除水中溶解态腐殖酸研究

本文以活性炭多维电极法，去除水中氯消毒副产物的前驱物－溶解态腐殖酸。文章比较了活性炭多维电极法与活性炭单纯吸附的去除效果，讨论了水样pH值、Ca^2 浓度、外电压、活性炭粒径和加入量对去除效果的影响。     

The Effect of Ozonation on the Removal of Organics by Coagulation – Flocculation

We present here some works which take place in the particular framework of the study of drinking water treatment of reservoir waters which contain high concentrations of organics, mainly humic substances. Previous studies on coagulation of fulvic acid solutions have proved that the optimal removal of organic matter was reached at acidic pH with 2 mg of ferricion per mg or organic carbon (summarized in this paper). The main question in this study is to know what is the impact of preozonation on the removal of organics by iron (III) coagulation.

The study of the behavior of organics, in terms of UV-absorbance and TOC measurements was made on three aquatic fulvic acids and on two raw waters. The experiments carried out with fulvic acids showed that preozonation (at 0.5 mg O₃/mg C) of fulvic acid appeared to have shifted the region of the optimal DOC removal towards the higher coagulant dose. Furthermore, increasing ozone doses led to a slight decreasing of coagulation efficiency at constant coagulant dose. With two raw waters, preozonation at low ozone doses (0.2 mg 0₃/mg C) was found to improve very slightly the elimination of organic matter, while high ozone doses (0.9 mg O₃/mg C) led to a disturbance of TOC elimination by iron coagulation.     

The Effect Of Preozonation On The Control Of Trihal Omethane Formation

A study was made to obtain a better understanding of the manner in which preozonation affects trihalomethane (THM) formation with respect to humic acid, citric acid, and 11 aromatic compounds which were components of humic acid, all in dilute aqueous medium. Ozonation before chlorination is able tonotonly decrease, butalso increase the concentrations of THM precursors. The compounds which are inherently high THM precursors, such as resorcinol, aniline, salicyl-aldehyde, phenol, andp-hydroxybenzoic acid, are controlled with respect tothe increase inthe amount ofozone consumed, but the compounds which have essentially no or alow potential for chloroform formation, such as hydroquinone. salicylic acid, methoxybenzene. benzaldehyde. and benzole acid, produce their maximum THM levels at a certain value of ozone consumed. When 1mg of organic carbon consumes more than 8 mg of ozone, THM formation from thetested aromatic compounds isdepressed by ozone.

Aliphatic carbonyl compounds which are the products resulting from the ozonation of aromatic compounds are not significant THM precursors. The preozonation of humic acid is not as effective in reducing its THM formation potential (THMFP) as when simple aromatic compounds are treated. However, the organic materials in the effluent from a biological treatment process usually have a high THMFP, in comparison with organic compounds which are contained in raw wastes. Therefore, there is a limitation in the effectiveness of utilizing biological treatment to remove the precursors of THM.     

生物活性炭对含吲哚和吡啶废水的去除研究

考察了三种不同生物活性炭对含吲哚和吡啶的模拟废水的去除效果。三种生物活性炭由沥青基球形活性炭（PSAC）、煤质柱状炭（EAC）和椰壳颗粒炭（GAC）循环挂膜制得,分别简称B-PSAC、B-EAC和B-GAC。生物活性炭的运行可分为三个阶段,活性炭的吸附阶段、活性炭的挂膜阶段以及生物活性炭阶段,考察指标为吲哚和吡啶的浓度。结果表明：三种生物活性炭对吲哚的去除率都在96%以上;B-GAC对吡啶的去除率最好,一般在90%以上,B-PSAC次之,约为75%,B-EAC去除效果最差。