Removal potential of anti-estrogenic activity in secondary effluents by coagulation

Anti-estrogenic activity in wastewater is gaining increased attention because of its endocrine-disrupting function. In this study, the level and removal efficiency by coagulation of anti-estrogenic activity in secondary effluents of domestic wastewater treatment plants were studied. Anti-estrogenic activity was detected in secondary effluent samples at a tamoxifen (TAM) equivalent concentration level of 0.38–0.94 mg-TAM L⁻¹. Dissolved organic matters (DOM) with the molecular weight (MW) less than 3000 Da in hydrophobic acids (HOA) and hydrophobic neutrals (HON) fractions of the secondary effluent were the key fractions related to anti-estrogenic activity. Coagulation with FeCl₃ and polyaluminium chloride (PAC) can remove the anti-estrogenic activity of the secondary effluents, but the removal efficiency was limited. The removal efficiency using FeCl₃ coagulant was higher than that induced by PAC. Dissolved organic carbon was continuously removed with increased coagulant dose (0–120 mg L⁻¹ FeCl₃ or 0–60 mg L⁻¹ PAC). However, the removal of anti-estrogenic activity was not enhanced further when the coagulant concentration was beyond a critical value (30 mg L⁻¹ FeCl₃ or 10 mg L⁻¹ PAC). The highest removal of anti-estrogenic activity was about 36% by FeCl₃ and 20% by PAC. Size exclusion chromatography results indicated difficulty in removing DOM with MW less than 3000 Da in the secondary effluent during coagulation even at a high coagulant concentration, which led to low removal efficiency of anti-estrogenic activity.     

Aniline and 2,4,6-trinitrotoluene associate preferentially to low molecular weight fractions of dissolved soil organic matter

Aniline and 2,4,6-trinitrotoluene (TNT) were equilibrated with particulate (POM) and dissolved organic matter (DOM) from an organic soil at different compositions of adsorbed major cations (Na, Al) and pH (aniline: 3.7–5.1, TNT: 4.8–5.0). After separation of POM, concentrations of ¹⁴C-labelled aniline and TNT* (including TNT degradation products) were determined in DOM size fractions using size-exclusion chromatography (SEC) and UV-detection. Concentrations in the <3.5 kDa size fraction were 2.8–6.0 and 8.5–9.5 times higher for aniline and TNT*, respectively, as compared to the >40 kDa fraction. Thus, both aniline and TNT* were preferentially associated to the smallest DOM size fraction. The significant binding to DOM (similar extent as to POM) and the fact that the <3.5 kDa DOM fraction was less susceptible to flocculation by major metals suggests that the mobility of aniline and TNT is highly affected by the solubility of soil organic matter.     

Removal of Cr(VI) and humic acid by using TiO2 photocatalysis

The removal efficiencies of Cr(VI) and HA, using a TiO(2)-mediated photocatalytic process, were investigated with variations in the pH, TiO(2) dosage and Cr(VI)/HA ratio. During the photocatalytic reaction, the total removal of Cr(VI) occurred through adsorption onto TiO(2), as well as its reduction to Cr(III). However, oxidation and adsorption were identified as important removal processes for the treatment of HA. Due to the anionic type adsorption onto TiO(2) and its acid-catalyzed photocatalytic reduction, the removal of Cr(VI) decreased with increasing pH, while that of HA increased with increasing pH. The TiO(2) dosage was also an important parameter for the removal of Cr(VI). As the TiO(2) dosage was increased to 2.5 g l(-1), the removal of Cr(VI) was continuously enhanced, but decreased at dosages above 3 g l(-1) due to the increased blockage of the incident UV light used for the photocatalytic reaction. The removal of Cr(VI) was greatly enhanced when the system contained both HA and Cr(VI) compared to Cr(VI) alone. Also, the removal of HA was greatly enhanced when the system contained both HA and Cr(VI) compared to HA alone. The removal of Cr(VI) was continuously enhanced as the HA concentration gradually increased; however, no further increase was observed above 20 mg l(-1) HA due to the increased absorption of the UV light. This result supports that the photocatalytic reaction, with illuminated TiO(2), could be applied to more effectively treat wastewater containing both Cr(VI) and HA than that containing a single species only.     

Spectroscopic study of the degradation of antibiotics and the generation of representative EfOM oxidation products in ozonated wastewater

This study examined effects of ozonation on thirteen fluoroquinolone, macrolide and lincosamide antibiotics present in municipal wastewater. Transformations of effluent organic matter (EfOM) caused by ozonation were characterized using absorbance/fluorescence spectroscopy and high performance size exclusion chromatography (HPSEC). Concentrations of aldehydes and carboxylic acids generated via the oxidation of EfOM were also determined. The absorbance and fluorescence of ozonated wastewater decreased with increasing ozone dose or treatment time. HPSEC data showed that these phenomena corresponded to the oxidation of all EfOM fractions, with some preference towards the degradation of the EfOM molecules with high apparent molecular weight. The removal of antibiotics and production of aldehydes and carboxylic acids were strongly correlated with the changes in both EfOM absorbance and fluorescence. Applications of a model describing the concurrent degradation of trace level contaminants and relative changes of EfOM emission allowed achieving a good fitting between the experimental and modeled ΔC/C₀ vs. ΔA/A₀ and ΔC/C₀ vs. ΔF/F₀ data.     

硅藻土强化混凝去除微污染原水中的有机物

研究了联用硅藻土与聚合氯化铝（PAC）强化混凝对有机微污染原水中不同性质溶解性有机物的去除效果。采用超滤膜和XAD系列树脂对微污染原水中溶解性有机物进行分级表征,物理分级表明分子量〈4 kD的溶解性有机物占50%以上,化学分级表明原水中以憎水酸（HoA）和亲水物质（HiM）为主。硅藻土助凝去除溶解性有机物,实验结果表明,当PAC投加量30 mg/L,硅藻土投加量0.5 g/L时,溶解性有机碳去除率由22.5%提高到26.3%。     

Quantifying the influence of humic acid adsorption on colloidal microsphere deposition onto iron-oxide-coated sand

This article describes an approach for quantifying microsphere deposition onto iron-oxide-coated sand under the influence of adsorbed Suwannee River Humic Acid (SRHA). The experimental technique involved a triple pulse injection of model latex microspheres (microspheres) in pulses of (1) microspheres, followed by (2) SRHA, and then (3) microspheres, into a column filled with iron-coated quartz sand as a water-saturated porous medium. A random sequential adsorption model (RSA) simulated the gradual rise in the first (microsphere) breakthrough curve (BTC). Using the same model calibration parameters a dramatic increase in concentration at the start of the second particle BTC, generated after SRHA injection, could be simulated by matching microsphere concentrations to extrapolated RSA output. RSA results and microsphere/SRHA recoveries showed that 1 μg of SRHA could block 5.90 ± 0.14 × 10⁹ microsphere deposition sites. This figure was consistent between experiments injecting different SRHA masses, despite contrasting microsphere deposition/release regimes generating the second microsphere BTC.     

TiO2光催化氧化脱除模拟烟气中的NOx

采用P25纳米TiO2为催化剂,对NOx浓度360 mg/m3的模拟烟气进行了光催化氧化实验研究,以期为此种方法在电厂烟气脱硝方面的应用提供依据。经SEM、XRD等表征手段,探讨了催化剂晶型尺寸对光催化的作用。实验考察了光催化反应过程规律以及负载量、光照度、NO初始浓度、O2含量、相对湿度和停留时间对光催化氧化效率的影响。结果表明,光催化反应是瞬态到稳态的过程,其催化效率与上述影响因子有密切关系。实验最优条件下NOx的脱除率为46%,但只需适当提高氧化效能,便能达到理想的效果。     

TiO2光催化对微滤去除腐殖酸的膜污染控制研究

着重研究了不同紫外灯光源和照射时间条件下,TiO2光催化（PCO）对微滤去除腐殖酸过程中的膜污染控制,并探讨了膜污染的控制机理。研究结果表明,TiO2光催化能有效提高微滤对腐殖酸的去除,同时降低膜通量的下降,起到有效控制膜污染的作用。进一步的实验分析表明,TiO2光催化控制膜污染的主要机理在于将腐殖酸降解为易于被TiO2吸附的小分子量物质,吸附腐殖酸降解产物后的TiO2聚合颗粒粒径增大,易于在膜表面形成更为松散的沉积层,并使膜污染从以膜孔堵塞和沉积层污染为主转化为以沉积层污染为主的可逆性污染。     

Influences of redox transformation, metal complexation and aggregation of fulvic acid and humic acid on Cr(VI) and As(V) removal by zero-valent iron

This study investigated the removal kinetics and mechanisms of Cr(VI) and As(V) by Fe(0) in the presence of fulvic acid (FA) and humic acid (HA) by means of batch experiments. The focus was on the involvements of FA and HA in redox reactions, metal complexation, and iron corrosion product aggregation in the removal of Cr(VI) and As(V) removal by Fe(0). Synthetic groundwater was used as the background electrolyte to simulate typical groundwater. The results showed faster Cr(VI) removal in the presence of HA compared to FA. Fluorescence spectroscopy revealed that no redox reaction occurred in the FA and HA. The results of the speciation modeling indicate that the free Fe(II) concentration was higher in the presence of HA, resulting in a higher removal rate of Cr(VI). However, the removal of As(V) was inhibited in the HA solution. Speciation modeling showed that the concentration of dissolved metal-natural organic matter (metal-NOM) complexes significantly affected the aggregation of the iron corrosion products which in turn affected the removal of As(V). The aggregation was found to be induced by gel-bridging of metal-NOM with the iron corrosion products. The effects of metal-NOM on the aggregation of the iron corrosion products were further confirmed by TEM studies. Larger sizes of iron corrosion products were formed in the FA solution compared to HA solution. This study can shed light on understanding the relationships between the properties of NOM (especially the content of metal-binding sites) and the removal of Cr(VI) and As(V) by Fe(0).     

Study on photocatalytic degradation of gaseous dichloromethane using pure and iron ion-doped TiO2 prepared by the sol-gel method

The synthesis of TiO₂ and Fe–TiO₂ by sol–gel method is demonstrated and characterized. The characterization of TiO₂ and Fe–TiO₂ is performed with instruments, including TGA/DTA, FTIR, UV–Vis, N₂ adsorption and SEM. Dichloromethane is used for the photocatalytic activity test. From the results of dichloromethane photocatalyitc degradation, the calcined temperature of TiO₂ and the presence of water vapor influence the photocatalytic activity. The optimum doping amount of iron ions is 0.005 mol%, and this can enhance the photocatalytic activity, while too great an amount will make the iron ions become recombination centers for the electron–hole pairs and reduce the photocatalytic activity. UV–Vis diffuse reflectance spectra of Fe–TiO₂ show an increase in absorbency in the visible light region with the increase in iron ions doping concentration The intermediate of dichloromethane photodegradation includes CHCl₃, CCl₄, CH₂Cl₂ and COCl₂. The presence of iron ions may reduce the adsorption of Cl element on the surface of the photocatalyst.     

Influence of ionic strength and pH on the limitation of latex microsphere deposition sites on iron-oxide coated sand by humic acid

This study, for the first time, investigates and quantifies the influence of slight changes in solution pH and ionic strength (IS) on colloidal microsphere deposition site coverage by Suwannee River Humic Acid (SRHA) in a column matrix packed with saturated iron-oxide coated sand.Triple pulse experimental (TPE) results show adsorbed SRHA enhances microsphere mobility more at higher pH and lower IS and covers more sites than at higher IS and lower pH. Random sequential adsorption (RSA) modelling of experimental data suggests 1 μg of adsorbed SRHA occupied 9.28 ± 0.03 × 10⁹ sites at pH7.6 and IS of 1.6 mMol but covered 2.75 ± 0.2 × 10⁹ sites at pH6.3 and IS of 20 mMol. Experimental responses are suspected to arise from molecular conformation changes whereby SRHA extends more at higher pH and lower ionic strength but is more compact at lower pH and higher IS. Results suggest effects of pH and IS on regulating SRHA conformation were additive.     

铂铈共掺杂纳米TiO2的制备、表征及光催化性能

以钛酸四丁酯为前驱体,过氧化氢为氧化剂,采用简单易行的低温氧化法制备出晶粒尺寸较小（平均尺寸25nm）的二氧化钛纳米粒子。通过贵金属Pt掺杂TiO2（Pt-TiO2）、稀土元素Ce掺杂TiO2（Ce-TiO2）和Pt、Ce共掺杂TiO2（Pt／Ce-TiO2）的掺杂的方法对二氧化钛进行改性。通过XRD,XPS,TEM,紫外漫反射等表征手段对制备的样品进行表征。通过可见光下降解罗丹明B来测试其光催化活性。实验结果表明,由ce掺杂的TiO2光催化剂对有机污染物的最大降解能力略大于Pt掺杂的TiO2,2种元素进行共同掺杂时对应的TiO2光催化剂降解能力最大。     

TiO2/GeO2复合膜光催化氧化降解农药废水的研究

提出了一种新的TiO2/GeO2复合膜圆形光催化氧化反应器,研究了该反应器对经物化处理后的农药废水进行降解的过程。研究表明,光催化氧化的最佳条件是锌片镀TiO2/GeO2复合膜、pH=6.7、过氧化氢（H2O2）浓度为400 mg/L。并对其他氧化剂对该过程的影响进行了探讨。有机废水通过该反应器处理后,其COD值降为57mg/L。能使有机污染物全部降解为小分子无机物,废水达到国家一级排放标准。     

介孔TiO2的制备及光催化降解有机染料的研究

以十六烷基三甲基溴化胺为模板剂,用溶胶-凝胶法制备了介孔TiO2,用x射线衍射、透射电子显微镜、热重/差热分析及氮气吸附等方法对其进行了分析表征,并用偶氮染料阳离子红X-GRL为目标污染物分析了它的光催化活性.实验结果表明,450℃热处理后的介孔TiO2是锐钛矿型的,平均孔径为18 nm.氮气吸附曲线呈典型的介孔材料Ⅳ型吸附等温线特征.由于介孔TiO2具有较大的比表面积,因此表现出比非介孔TiO2高的光催化活性.     

Tracing the sources of refractory dissolved organic matter in a large artificial lake using multiple analytical tools

Structural and chemical characteristics of refractory dissolved organic matter (RDOM) from seven different sources (algae, leaf litter, reed, compost, field soil, paddy water, treated sewage) were examined using multiple analytical tools, and they were compared with those of RDOM in a large artificial lake (Lake Paldang, Korea). Treated sewage, paddy water, and field soil were distinguished from the other sources investigated by their relatively low specific UV absorbance (SUVA) values and more pronounced fulvic-like versus humic-like fluorescence of the RDOM samples. Microbial derived RDOM from algae and treated sewage showed relatively low apparent molecular weight and a higher fraction of hydrophilic bases relative to the total hydrophilic fraction. For the biopolymer types, the presence of polyhydroxy aromatics with the high abundance of proteins was observed only for vascular plant-based RDOM (i.e., leaf litter and reed). Molecular weight values exhibited positive correlations with the SUVA and the hydrophobic content among the different RDOM, suggesting that hydrophobic and condensed aromatic structures may be the main components of high molecular weight RDOM. Principal component analysis revealed that approximately 77% of the variance in the RDOM characteristics might be explained by the source difference (i.e., terrestrial and microbial derived) and a tendency of further microbial transformation. Combined results demonstrated that the properties of the lake RDOM were largely affected by the upstream sources of field soil, paddy water, and treated sewage, which are characterized by low molecular weight UV-absorbing and non-aromatic structures with relatively high resistance to further degradation.     

TiO2-rGO制备及其对亚甲基蓝溶液的降解

本实验用改进的Hummers法制备氧化石墨烯(GO),通过溶胶-凝胶法制备得到TiO2-石墨烯复合材料(TiO2-rGO),研究了不同制备条件对复合材料光催化性能的影响。采用X射线衍射(XRD),拉曼光谱(Raman),比表面积(BET),扫描电镜(SEM),透射电镜(TEM)、紫外-可见(UV-Vis)吸收光谱和荧光光谱(PL)等测试手段对复合材料进行表征。结果表明,TiO2-rGO复合材料中的TiO2为锐钛相,且能均匀附着在石墨烯片层上,呈现层状堆积结构;与纯TiO2相比,复合材料具有较大的比表面积和更高的可见光响应。研究了该复合催化剂在紫外光下对亚甲基蓝以降解效果。当焙烧温度为450℃、TiO2/GO质量比为125:1时,制备得到的TiO2-rGO具有最优的光催化效果。     

MBR工艺中溶解性有机物的分子量和EEM解析

采用凝胶过滤色谱(GFC)分子量测定技术和三维荧光(EEM)光谱技术,对平板膜-生物反应器工艺应用于餐饮废水和粪便污水处理的工程实例进行研究,对比分析2套工艺中的调节池水和出水的溶解性有机物(DOM)及污泥胞外聚合物(EPS)的性质变化.研究表明,餐饮废水处理过程的调节池水DOM中大分子(＞100 kDa)物质比例为6...     

Determination of 10 particle-associated multiclass polar and semi-polar pesticides from small streams using accelerated solvent extraction

A new analytical method using accelerated solvent extraction was developed for the determination of 10 particle-associated polar and semipolar pesticides. In addition, six deuterated analogues of the target compounds were evaluated as internal standards. The method yielded acceptable accuracy (73–103% recovery) and precision (<25% relative standard deviation) for eight compounds. Using size exclusion chromatography (SEC) as cleanup step resulted in higher recoveries compared to solid phase extraction (SPE) cleanup.

Deuterated standards with 10 or more deuterium atoms performed well as internal standards concerning similar recovery and correlation with the target analytes.

The method was employed to extract particle-associated pesticides from 16 streams located in an area with intense agriculture in France. Acetochlor, pirimicarb, tebuconazole, fenpropidin, -endosulfan and chlorfenvinphos were detected at concentrations up to 1 mg kg⁻¹ dry weight. A comparison with aquatic toxicity data indicated potential risk to the benthic fauna exposed to these concentrations of pirimicarb, -endosulfan and chlorfenvinphos.

We suggest that the method presented here be used for the extraction and quantitation of particle-associated polar pesticides.     

切削液废水处理过程中溶解性有机物分子质量分布和光谱特征的转化规律

以隔油-混凝沉淀-水解酸化-好氧共代谢为组合工艺处理切削液废水,探究各处理单元对不同种类有机物的转化规律和去除能力;对各处理单元出水中的溶解性有机物(DOM),采用超滤膜法进行分子质量分级,应用紫外-可见吸收光谱、三维荧光光谱等方法对各单元出水及其滤后液进行了分析。结果表明,隔油池出水DOM分子质量主要分布在<1 kDa小分子质量区间和>100 kDa的大分子质量区间,分子质量占比分别为46.04%、42.79%,混凝沉淀对大分子质量的DOM有较好的去除效果,混凝沉淀出水、水解酸化池出水、好氧池出水的DOM主要分布在<1 kDa区间。切削液废水处理过程中出现5个荧光峰,其中峰A和峰B可能为多环芳香烃和杂环化合物的混合物;峰C为石油类;峰D可能是废切削液中滋生的微生物和细菌的细胞物质及其分泌物或单环芳香烃;峰E可能为杂环化合物或多环芳烃类腐殖酸。经一级处理(隔油和混凝沉淀)后峰A和峰B的去除率分别为60%和35%;峰C和峰D去除率均大于99%。经二级处理(水解酸化和好氧共代谢),峰A和峰B的去除率分别为23%和48%。该工艺流程对切削液废水中的有机物有较好的去除效果,石油类、COD、TOC、BOD₅的总去除率可达99.99%、98.81%、98.74%、99.78%,达到了《污水排入城镇下水道水质标准》中的B级标准。