Photobleaching mechanisms of Radachlorin photosensitizer in aqueous solution

The time dependence of the fluorescence intensity of aqueous solutions of Radachlorin photosensitizer at different concentrations and the influence of the dissolved oxygen concentration on the fluorescence dynamics are analyzed. The experimental results are interpreted based on the numerical solution of the system of kinetic equations describing the photochemical processes that lead to the formation and degradation of singlet oxygen in solution. The influence of possible mechanisms of photosensitizer photobleaching is analyzed. It is shown that the main photobleaching mechanism under our experimental conditions is the chemical reaction between the photosensitizer in the triplet state and dissolved oxygen molecules. Two rate constants of electron-transfer chemical reactions, which are important for understanding the nature of the occurring photoprocesses, are determined.     

The use of dosimeters to measure radical production in aqueous sonochemical systems

The use of two dosimeter systems for quantifying radical production during aqueous sonochemical processes has been investigated. The Fricke (Fe²⁺/Fe³⁺) system was found to be useful at higher concentrations but care must be taken in interpreting the results since radical production is not the only process taking place. There is some reaction even in the absence of ultrasound and this involves dissolved oxygen gas. The concentration of hydroxyl radicals formed was accurately monitored at low concentrations using the terephthalate dosimeter and the limits of its applicability were found. Both systems were used to investigate the effect of varying the ultrasound intensity.     

Dosimetry in sonochemistry: the use of aqueous terephthalate ion as a fluorescence monitor

The generation of HO radicals by acoustic cavitation in water was monitored by their reaction with terephthalic acid (TA) anion to produce fluorescent hydroxyterephthalate ions using a cleaning bath (38kHz) and a probe system (20, 40 and 60 kHz) as different sources of ultrasound. When using the ultrasonic bath as a source of energy for sonochemical studies, the shape of the reaction vessel is important. In the case of HO production from water (50 cm³), reaction in a conical flask (100 cm³) produces 2.75 times more radicals than a round-bottomed flask of the same capacity. The fluorescence yield (fluorescence intensity/ultrasound dosage) obtained using the conical flask and ultrasonic bath was similar to that for a probe operating at 40 kHz on the same volume of solution. For a probe system operating at 20, 40 and 60 kHz the greatest sonochemical efficiency was attained at the highest of these frequencies (60 kHz). For the probe system the fluorescence yield is directly proportional to power input and the concentration of TA. The fluorescence yield decreases as the temperature is increased.     

The effect of dissolve gas concentration in the initial growth stage of multi cavitation bubbles. Differences between vacuum degassing and ultrasound degassing

The sonochemical luminescence intensity from luminol was measured at a sampling rate of several kilohertz. This was noted at three different periods: first, the latent period in which no light emission occurs at all; second, the increased emission period from the start of light emission to the time when a steady state is reached; and third, the steady state period in which light emission occurs at the steady state value. When irradiated with ultrasound of different intensities, the times of the latent period and increased emission period are shorter for higher ultrasound intensities. To know how the dissolved oxygen content is involved in early-stage cavitation growth, an experiment was conducted using solutions with varying dissolved oxygen contents from 100% to 37%. For dissolved air content of 50% or less, it was found that the latent period was 30 times longer in a saturated condition. It was also found that the increased emission period was 10 times longer. However, the emission intensity in the steady state did not change at all even when the initial dissolved gas concentration of the sample was changed. From this, it was found that the reuse of collapsed bubbles takes place efficiently in the steady state. Dissolved oxygen was reduced by the use of a vacuum pump and by the degassing action of ultrasound, and it was discovered that the behavior of transient emission differed for the two ways of degassing.     

Zinc-8-hydroxyquinoline intercalated in calcium bentonite: A promising DO sensor

Zn(II) and 8-hydroxyquinoline were made to react in an in situ solid−solid reaction in the interlayer space of Ca-bentonite from Thailand, resulting in [Zn(8-hydroxyquinoline)₂]²⁺, the well known -Znq₂. X-ray diffraction patterns showed that the interlayer space of the bentonite increased from 1.56 to 1.67 nm on going from Zn(II)-bentonite to Znq₂-bentonite, which confirmed the intercalation of Znq₂ in bentonite. The intercalated Znq₂-bentonite compound was mixed with a solution of polystyrene in toluene and coated as a film on a polystyrene sheet. The fluorescence intensity of Znq₂-bentonite film was measured in the presence of dissolved oxygen (DO). It was found that the fluorescence intensity of the film decreased as dissolved oxygen increased, which is a promising result for developing an optical dissolved oxygen sensor (DO sensor). The fluorescence quenching by oxygen followed the Stern-Volmer plot.     

应用于FAGE技术测量OH自由基的激光器波长修正方法研究

研究了一种应用于气体扩张激光诱导荧光(FAGE)技术测量OH自由基的染料激光器波长修正方法。该方法采用镍铝丝热解水汽产生稳定的高浓度OH自由基,利用重复频率为8500 Hz的染料激光器输出波长约282 nm激光作为光源.激发低压腔内热解产生的高浓度高稳定性OH自由基产生荧光,由普通光电倍增管和光电二极管分别探测激发荧光和出腔激光强度。通过延时信号发生器统一触发激光器和高速数据采集卡并结合LabVIEW软件处理得到单位激光强度的荧光积分强度数据。连续两次扫描激光波长,当第二次扫描的荧光积分强度达到第一次最大值的0.95倍时,停止波长扫描,此时的激光器波长位置即为激发线位置。本文首先扫描激光波长,研究了282 nm激发机制下的OH自由基激发谱;然后在Q_1 2激发线位置探究了气体湿度、氧气含量、进气量以及抽速对荧光积分强度和寿命的影响;并分析了镍铝丝热解水的反应机理,初步认为热解中OH自由基主要来源于氧原子与水的反应。在以上荧光积分强度和寿命影响因素的研究基础上,优化了系统参数,使荧光积分强度波动小于±1.9%。连续多次进行波长修正,修正偏差为0.1pm。该方法能够满足气体扩张激光诱导荧光(FAGE)技术定量精确测量大气OH自由基对波长的要求。     

基于单光源频域荧光寿命的水体溶解氧浓度检测方法

现有的光学溶解氧浓度检测方法中光路及电路结构复杂,本文提出了一种单路光源的频域荧光寿命的溶解氧检测方法.采用单路光源的光学结构实现水体溶解氧浓度的检测,简化了光路及电路结构,改进了溶解氧浓度检测算法,降低了整体检测过程的计算量.设计对比实验对方法进行验证,实验结果表明:单光源的频域荧光寿命的检测方法与DOP1光学溶解氧分析仪相比,在0~9mg/L范围内,实际检测误差降低至0.04mg/L;衡量稳定性的检测标准偏差为0.007mg/L,同比降低了36%;采用快速傅里叶变换以及改进的溶解氧浓度计算方法,配合优化的电路及光路结构,在达到90%稳态时响应时间平均缩短了12s,浓度上升和下降时的响应速度分别提升为40%和28%.该方法具有较好的检测精度、稳定性以及响应速度.     

不同水体中有色可溶性有机物质荧光光谱定量分析研究

有色可溶性有机物(CDOM)是指水体中对紫外及可见光均有光吸收的溶解有机物,能对水色产生影响,是自然生态系统、水色光学遥感、水体碳循环研究中必不可少的环境因素。由于CDOM具有荧光特性,荧光光谱技术已成为开展CDOM研究的重要手段,被用于CDOM的来源、分布及其变化规律的研究。文章主要利用荧光检测技术,研究了不同水体CDOM的发射荧光光谱峰面积、荧光峰强度与其浓度间的变化关系,发现在低浓度范围内,发射光谱峰面积和荧光强度与CDOM浓度具有良好的线性关系(r2＞0.98);不同浓度的CDOM水溶液的发射光谱峰面积及其荧光强度随浓度的变化趋势是一致的。文章首次利用低浓度下CDOM的发射光谱峰面积与浓度间的线性关系,建立了适合于水体中组成复杂的CDOM的定量分析方法,拓展了荧光分析技术在CDOM研究中的应用。     

Frequency and power dependence of ultrasonic degassing

We investigated the time variation of ultrasonic degassing for air-saturated water and degassed water with a sample volume of 100 mL at frequencies of 22, 43, 129, 209, 305, 400, 514, 1018, and 1960 kHz and ultrasonic power of 15 W. Ultrasonic degassing was evaluated by dissolved oxygen concentration. Ultrasonic degassing was also investigated at a frequency of 1018 kHz and ultrasonic powers of 5, 10, 15, and 20 W. The dissolved oxygen concentration varied with the ultrasonic irradiation time and became constant after prolonged ultrasonic irradiation. The constant dissolved oxygen concentration value depended on the frequency and ultrasonic power but not the initial dissolved oxygen concentration. The degassing rate at 101.3 kPa was higher in the frequency range of 200 kHz to 1 MHz. The frequency dependence of the degassing rate was almost the same as that of the sonochemical efficiency obtained by the potassium iodide (KI) method. Ultrasonic degassing in the frequency range of 22–1960 kHz was also investigated under reduced pressure of 5 kPa. Degassing was accelerated when ultrasonic irradiation was applied under reduced pressure. However, under a reduced pressure of 5 kPa, the lower the frequencies, the higher is the degassing rate. The sonochemical reaction rate was examined by the KI method for varying dissolved air concentrations before ultrasonic irradiation. Cavitation did not occur when the initial dissolved oxygen concentration was less than 2 mg·L⁻¹. Therefore, the lower limit of ultrasonic degassing under 101.3 kPa equals 2 mg·L⁻¹ dissolved oxygen concentration. A model equation for the time variation of dissolved oxygen concentration due to ultrasonic irradiation was developed, and the degassing mechanism was discussed.     

污染水体溶解有机物诱导荧光猝灭特性的实验研究

溶解有机物的含量是衡量水质的常用指标,利用荧光方法可以实现对自然水体溶解有机物的浓度进行高灵敏在线遥测。文章利用三维荧光光谱技术对溶解有机物进行了荧光表征,实验研究了溶解有机物浓度与荧光强度的关系,以及水体酸碱度和金属离子对荧光强度的影响。研究表明,当溶解有机物浓度在小于10 mg·L-1,pH值在6.5～7.5范围内时,荧光强度与浓度具有很好的线性关系;金属离子对溶解有机物诱导荧光有较大猝灭作用,不同金属离子对诱导荧光强度的猝灭效果有显著不同。     

一种溶解氧敏感膜荧光发射效率光谱检测系统的研制

荧光猝灭法是快速测量污水、地表水以及渔业养殖水环境中溶解氧含量的先进技术之一,氧敏感膜是荧光猝灭法检测技术的核心,高荧光发射效率的氧敏感膜具有灵敏度高、特异性强、信噪比高的优点,检测结果更为准确。高效率是优选氧敏感膜的依据,也是溶解氧检测元器件、检测电路和检测光路优化设计的关键。现有溶解氧荧光检测装置中未有对氧敏感膜进行质量评估的标准方法,基于对已有传感器探头光路和电路的研究,该研究分析了全波段的荧光发射效率,选用大功率氙灯作为激发光源,基于连续单波长逐级扫描进行单色分光,构建了氧敏感膜的激发光-荧光光谱扫描装置,然后通过扫描测定氧敏感膜的激发光光谱和荧光光谱,提出并建立了荧光发射效率计算方法,提出的方法能客观地评估荧光发射能力,准确寻找最佳激发波长。为验证该方法的可行性,对来自国内外的多个氧敏感膜样品进行了实验测定,测试结果表明：单张氧敏感膜荧光发射效率随波长变化,呈多峰分布,同一型号的样品荧光效率曲线相似,但荧光发射效率差异较大,同一激发波长下荧光发射效率最大者较最小者高出14.5%,三张氧敏感膜的最大峰值波长均不同,分别为：401,543和435 nm,但发射峰值波长均为650 nm;不同型号的氧敏感膜相比较,最大荧光发射效率可相差1～2个数量级;实测传感器中使用的激发波长,其所选用的激发波长并非最大发射峰值波长,其荧光发射效率仅为最大荧光发射效率的1/2,表明传感器光源可以进一步优化选型。综上所述,本文建立了一种溶解氧敏感膜荧光发射效率检测系统,提出了以荧光发射效率评估氧敏感膜的方法,并开展了相关实验测定。本文工作可望用于新型氧敏感膜材料、工艺的研究及传感器优化设计与制造。     

水体中溶解有机物激光诱导荧光光谱分析方法

讨论了用激光诱导荧光(LIF)的方法分析水体中溶解有机物(DOM)的含量,利用拉曼散射信号对荧光光谱进行归一化处理,消除激发光强度和水体对荧光的二次吸收和接收条件等因素的影响,并给出了理论依据,由此依据得出了非线性浓度校准的数学模型。利用这个数学模型对实验数据进行非线性拟合,拟合的相关系数高于0.99。该浓度校准的数学模型,考虑到了水体对荧光信号的二次吸收以及溶液浓度的变化对二次吸收的影响,结果表明它可作为不同水体的通用浓度校准的数学模型对水体中的DOM进行定量分析。     

不同溶解氧水平上覆水中DOM荧光特性及总氮含量评估

采用荧光光谱技术研究不同溶解氧(DO)水平下二十埠河底泥上覆水中溶解性有机物(DOM)转化特性及类蛋白荧光强度与总氮浓度的关系。三维荧光光谱显示：上覆水中DOM主要由三种类蛋白物质(高激发波长类酪氨酸、低激发波长类酪氨酸、低激发波长类色氨酸)和两种类富里酸物质(紫外区类富里酸、可见区类富里酸物质)组成,类蛋白物质是上覆水中DOM的主要成分。经过曝气后类蛋白荧光强度均存在明显降低,其中低激发波长酪氨酸和低激发波长色氨酸相对于高激发波长酪氨酸更易被微生物降解。而类富里酸荧光强度则均呈现增强趋势,表明类富里酸物质属于难降解有机物。上覆水中DOM荧光指数介于1.65~1.8之间,表明上覆水体DOM既有陆源又有生物源但以生物源为主。荧光指数随DO增加而增大,说明随着DO增加微生物量及微生物活性逐渐增加,微生物代谢功能增强,使得上覆水中DOM的生物源成份加大。在较高的溶解氧水平下,即DO分别为2.5,3.5和5.5 mg·L-1时,高激发波长类酪氨酸峰A的荧光强度与上覆水中总氮浓度有良好的相关性,相关系数(r2)分别为0.956,0.946,0.953,说明可以通过三维荧光技术监测高激发波长类酪氨酸峰A的荧光强度而快速分析上覆水中总氮浓度,为河道水体诊断、治理及修复提供快速有效的技术参考和理论支持。     

不同水体中溶解有机物的荧光光谱特性研究

用激光诱导荧光(laser induced fluorescence, LIF)方法对几种不同水体中溶解有机物(dissolved organic matter, DOM)的荧光光谱进行了测量和分析,给出了不同浓度腐殖酸的归一化荧光强度与浓度的关系。结果表明, 可用此种方法进行有效的水体质量监测。     

Quantification of ultrasonic intensity based on the decomposition reaction of porphyrin

A simple method is proposed for quantification of the effective ultrasonic intensity in the reaction vessel based on the decomposition reaction of 5,10,15,20-tetrakis(4-sulfotophenyl) porphyrin (H₂TPPS⁴⁻). The change of concentration of porphyrin in solution irradiated by the ultrasound wave depends on the irradiation time and the output power of ultrasound generator. The decomposition ratio of porphyrin is defined as the ratio of the concentration of porphyrin after ultrasonic irradiation to that before ultrasonic irradiation. A linear relationship between the decomposition ratio of porphyrin and the concentration Fe³⁺ in the Fricke solution under sonication was obtained. The decomposition ratio was related to the absorption dose in radiation chemistry.     

Synergistic effects of combining ultrasound with the Fenton process in the degradation of Reactive Blue 19

The decoloration of reactive dye C.I. Reactive Blue 19 (RB 19) using combined ultrasound with the Fenton process has been investigated. The effect of varying the concentrations of hydrogen peroxide and iron sulfate, initial pH, ultrasonic power, initial dye concentration and dissolved gas on the decoloration and degradation efficiencies was measured. Calibration of the ultrasound systems was performed using calorimetric measurements and oxidative species monitoring using the Fricke dosimeter and degradations were carried out with a 20 kHz probe type transducer at 2, 4, 6 and 8 W cm⁻² of acoustic intensity at 15, 25, 50 and 75 mg L⁻¹ initial dye concentrations. First order rate kinetics was observed. It was found that while the degradation rate due to ultrasound alone was slow, sonication significantly accelerated the Fenton reaction. While the results were similar to those reported for other dyes, the effects occurred at lower concentrations. The rate and extent of decoloration of RB 19 increased with rising hydrogen peroxide concentration, ultrasonic powers and iron sulfate concentration but decreased with increasing dye concentration. An optimum pH value of pH = 3.5 was found. The rate of decoloration was higher when dissolved oxygen was present as compared with nitrogen and argon confirming the solution phase mechanism of the degradation.     

不同环境氧浓度下聚甲氧基二甲醚（PODE）喷雾燃烧的羟基光谱分布及其反演重构研究

聚甲氧基二甲醚（PODE）是一种有潜力的柴油替代燃料，目前针对PODE的研究更多集中在发动机台架试验，相应的基础喷雾燃烧研究较少，制约了其在动力装置中高效清洁燃烧性能的提升。羟基（OH）性质活泼，大量存在的区域通常认为是高温反应区域。利用羟基光谱可以获得火焰结构、燃烧反应位置以及热释放速率等重要参数。环境氧浓度对火焰结构有很大影响，也是控制燃烧反应速率和污染物排放的重要参数。因此，在一台光学定容燃烧弹上，首先利用羟基的自发光光谱测量，研究了宽环境氧浓度变化（15%～80%）对PODE喷雾火焰浮起长度的影响，进一步利用阿贝尔逆变换方法将羟基自发光光谱强度由积分值反演为点位值，研究了富氧条件下（40%～80%）氧浓度变化对PODE喷雾羟基分布的影响。研究结果表明：环境氧浓度由15%增至40%，PODE火焰浮起长度迅速缩短；氧浓度进一步增加至80%，火焰浮起长度下降趋势逐渐变缓，直至基本不变；相同氧气浓度下PODE火焰浮起长度明显小于柴油。反演后的羟基光谱分布特征表面，富氧条件下PODE羟基光谱的高光强区域主要集中于喷雾边缘扩散火焰薄层中，同时，局部温度的显著提升使得羟基光谱强度在预混反应区下游附近达到最大；羟基光谱高光强区域随氧气浓度增加逐渐向火焰中上游区域迁移，并且其分布表现为轴向上更短，径向上更窄；在火焰达到准稳态时，相较40%氧气浓度条件，60%和80%氧气浓度下的羟基光谱强度在火焰中下游明显减弱，表明高的环境氧浓度下喷雾上游的燃油高浓度区域更快的参与到剧烈的燃烧反应中。     

水体中铬、镉和铅的X射线荧光光谱同时快速分析方法研究

以氢氧化钠和硫化钠为沉淀剂采用共沉淀法同时富集水体中的Cr,Cd和Pb,通过对Cr(OH)₃,Cd(OH)₂和PbS沉淀均匀悬浮液抽滤以制成Cr,Cd和Pb均匀分布的薄膜样品并进行能量色散XRF光谱测量,以实现水体中Cr,Cd和Pb的同时快速分析与检测。研究了富集过程中的反应时间和反应物摩尔比对薄膜样品XRF光谱强度的影响,确定了富集过程的最佳反应条件为沉淀反应时间为5 min,OH-与Cr3+的最佳摩尔比为5.0,OH-与Cd2+的最佳摩尔比为5.0,S2-与Pb2+的最佳摩尔比为2;对富集后不同浓度的薄膜样品进行了均匀性检验,富集区域6个不同位置荧光强度的相对标准偏差均小于4.8%,说明富集后的薄膜样品具有较好的均匀性;将不同浓度薄膜样品的理论浓度值与ICP-MS方法测得的浓度值进行对比分析,验证了该富集方法对水样中Cr,Cd和Pb的富集率均能达到90%以上;根据薄膜样品的荧光强度与ICP-MS测得的浓度值,建立了基于该富集方法的水体中Cr,Cd和Pb的X射线荧光光谱定量分析方法,Cr,Cd和Pb校准曲线的线性相关系数分别为0.997 3,0.995 0和0.999 8,当实际采集水样体积为50 mL时,Cr,Cd和Pb的检出限分别为7.4,29.6和8.5 μg·L-1,均低于《污水综合排放标准 GB 8978-1996》中Cr,Cd和Pb的最高允许排放浓度,因此该方法能够实现工业生产及生活排放污水中Cr,Cd和Pb的同时快速分析与检测。该研究为基于X射线荧光光谱法的水体多种重金属同时快速在线监测提供依据。     

Degradation of C.I. Acid Orange 7 by the advanced Fenton process in combination with ultrasonic irradiation

The combination of ultrasound and the advanced Fenton process (AFP, zero-valent iron and hydrogen peroxide) for the degradation of C.I. Acid Orange 7 was studied. The effect of hydrogen peroxide concentration, initial pH, ultrasonic power density, dissolved gas, and iron powder addition on the decolorization of C.I. Acid Orange 7 was investigated. A modified pseudo-first order kinetic model was used to simulate the experimental results. The results showed that the decolorization rate increased with the increase of hydrogen peroxide concentration and power density, but decreased with the increase of initial pH value. There existed an optimal iron powder addition when decolorization rate was concerned. The decolorization efficiency also increased with the increase of hydrogen peroxide concentration, but decreased with the increase of initial pH value. It varied little at different power densities or iron powder additions at the fixed hydrogen peroxide concentration. The presence of dissolved gas would enhance color removal, and the enhancement was more significant when dissolved oxygen was present. More hydrogen peroxide dosage and reaction duration are required to achieve a relatively high COD removal than those employed to simply break the chromophore group.